Cabboxylic acid abylides oe the benzene sebies and process oe making



Patented Apr. 18, 1933 UNITED STATES rarer 'FFICE.

micron]; LASKA AND osxan HALLnn. or OFFENBACH-OBI-THE-MAIN, GERMANY,- ASSIGNORS TO GENERAL ANILINE wear 1s, Inc, on NEW YORK, N. Y, A CORPORA- [PICK OF DELAWARE GABBOXYLIC ACID ARYLIDES or THE BENZENE snares AND r'aocnss on MAKING SAME No Drawing. Application filed October 23, 1929, Serial No. 401,972, and in Germany October 31, 19.28.

Our invention has for its object new carboxylic acid arylides of the benzene series and the process of making the same. The new compounds correspondto the following probable formula:

wherein X stands for a hydrogen atom or 2. nitro or methyl group, X and X stand for a hydrogen atom or a methyl group, and one Y stands for hydrogen and the other Y for a hydroxy group.

The new products are obtained by condensing in the first phase according to the process described in British Patent No. 5,444 of 1915 an aminocarboxylic acid of the benzene series with a hydroxycarboxylic acid of the benzene series and condensing the aroylaininoarylcarboxylic acid compounds thus formed or their acid chlorides, corresponding to the general formula X1 OH X2 wherein X and X stand for hydrogen atoms or methyl groups and Z for a hydroxy group or a chlorine atom, with an aminophenol compound, having at least one free orthoor para-position to the hydroxyl group. Both steps of the reaction may be advantageously carried out in presence of a dehydrating agent and of a diluent.

The same or analogous products are also obtained by at first condensing an aminophenol compound of the character described with an aminoor nitroarylcarboxylic acid or the corresponding acid chloride, reducing the condensation product, if necessary, and further condensing the amino compound thus formed with an aromatic carboxylic acid or 1ts chloride.

' The new compounds arein-theform-of groups. They are distinguished by theirv afiinity for the vegetable fiber whereby the impregnation of cotton goods with thenew products may be efiectedc In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, but we wish it to be understood that we are not limited to the particular products or reaction conditions mentioned therein. I i

a I Example 1 138 parts of salicylic acid and 137 parts'of p-aminobenzoic acid are suspended in about 2000 parts of toluene, then at about 7 0-80 C. slowly 60 parts of phosphorus trichloride are added and the mixture is heated at'about 110 until the evolution ofhydroch-loric acid gas ceases. The toluene is expelled from the I of its chloride) and 11' parts of m-amino phenol are suspended in-about D partsof dimethylaniline. Then at 70-80. G. 6 parts of phosphorus trichloride are slowly added is insoluble in the usual organic solvents. In order to purify this compound it may be dissolved in a caustic alkali solution, the solution may be boiled off with addition of animal charcoal and after filtration the new compound may be precipitated therefrom by introducing carbonic acid.

The course of reaction may be illustrated by the following scheme of equations about 8 hours. The reaction mass is worked up as described above. The m-cresoyl-maminobenzoic acid thus obtained of the formula coon crystallizes from glacial acetic acid and melts at about 280 while decomposing.

271 parts of this acid are then further condensed with 109 parts of m-aminophenol, preferably with addition of dimethylaniline. The condensation reaction and isolation of the reaction product are carried out as described in the foregoing example. The new condensation product thus obtained of the probable formula:

is insoluble in the usual organic solvents. In a pure state it melts at about 215. Accordso Qooon mngo o on= o ONH--O o OH+H20 on on Example 2 152 parts of m-cresotinic acid of the formula rue-G-o o o H and 137 parts of m-aminobenzoic acid are suspended in about 1200 parts of dimethylanllme. To the mixture at about '6070 (1, parts of phosphorus trichloride are added and finally the mixture is heated at about 110 for OH OH v H OH O 1,

ing to the same sequence of reaction steps by starting from 152 parts of m-cresotinic acid and 151 parts of 3-amino4-methylbenzene-1- carboxylic acid a condensation product of the probable formula COOH melting at 258261 is obtained, which yields, when 285 parts thereof are condensed with 109 parts of p-aminophenol, the mT-cresoyl-3- amino-t-methylbenzoyl-p-aminophenol of OH CH3 melting atabout 2404243 In the following table some further conden sat-ion products obtainable in a .similarman ner are named: I

Starting materials: 7

Condensation p roduct oi the first phase:

Condensed with:

I End product:

m-cresotinic acid and pm -cresoyl-p-aminobenzoicr acid of amlnobenzolc acid the formula: phenolroi the formula:

(3H5 (IJH:

I NH f IITH melting abot'e 350 0. IIIH" of about 245-247" melting point mkzresotinic ecid and mm-cresoyl-m-aminobenz0ic acid m-amino-o cresol of the m-cres0yl-m-aminqbenzoyl-m'-aminoaminobenzolc acid formu o'-cresol of the formula V see Example 2 v V NH: CH3

OH; no

| OH All 0 NH o-cresotinic ecidand paminobenzolc acid o'-cresoyl-p-aminobenzoic acid of the rmula l to 1 m (Boon of about 274 melting point m-aminophenol m-aminophencl m-cresoyl-p-ami.nobenzeyl m'- aminoof about 180-132 melting point o'-0resoyl -paminobenzoyl m'- aminophenol of the formula of about;2 93T294 melting point We claim: a V 1. As a new compound a carboxylicacid arylide corresponding to the probable folimula OH: o O-NHGOE HaCQCO-NHQ which compound is insoluble in the usual organic solvents, but is rendered soluble in water by the action of alkali.

2. The process which comprises condensing an amino-carboxylic acid of the formula:

/Y 'HzN- ooon with a carboxylic acid of the formula:

and combining by further condensation. the carboxylic acid group of the aroylaminoaryl-carboxylic acid thus formed with the amino group of an amino-hydroxy compound of the formula: V

and a diluent an amino-carboxylic acid of the formula:

X: with a carboxylic acid of the formula:

and combining by further condensation in the presence of a dehydrating agent and a diluent the, carboxylic acid group of the aroylamino-aryl-carboxylic acid thus formed with the amino group of an amino-hydroxy compound of the formula:

in which formulae X stands for a hydrogen atom, a nitro' or methyl group, X and X compound of the formula:

7 stand for hydrogenatoms or methyl groups,

and one Y stands for hydrogen and'the other Y for a hy QXy. g oup-V V 4. The process which comprises combining by condensation the carboxylic acid group of an aroyl-amino-aryl-carboxylic acid of the formula:

with the amino group of an amino-hydroxy compound of the formula:

in whichformulae X X and X stand for hydrogen atoms or methyl groups and Z stands for a hydroxy group or a chlorine atom.

5. The process which comprises combining by condensation in the presence of a dehydrating agent and a diluent the carboxylic acid group of an aroylamino-aryl b acid of the formula:

X1 H X1 002 with the amino group of an amino-hydroxy in which formulae X and X stand for hydrogen atoms or methyl groups and Z stands for a hydroxy group or a chlorine atom. 1

6. As new products, carboxylic acid arylides of the benzene series, corresponding to ;the following probable formula:

X Y X;

' V I goo-Nn cgx 3 wherein X stands for a hydrogen atom or a nitro or methyl group, X and X stand for a hydrogen atom or a methyl group, and one Y stands for hydrogen and the other Y for a hydroxy group, these products being insoluble in the usual organic solvents and in form of their alkali metal salts soluble in water, and distinguished by their affinity for the vegetable fiber.

7. As new products, carboxylic acid arylides of the benzene series, corresponding to the following probable formula:

wherein X stands for a hydrogen atom or a methyl group, these products being insoluble in the usual organic solvents and in form of their alkali metal salts soluble in water, and distinguished by their aifinity for the vegetable fiber.

8. As a new product, a carboxylic acid arylide corresponding to the following probable formula which product is insoluble in the usual organic solvents and in form of its alkali metal salts soluble in water, and distinguished by its aflinity for the Vegetable fiber.

9. As a new product, a carboxylic acid arylide corresponding to the following probable formula:

which product is insoluble in the usual organic solvents and in form of its alkali metal salts soluble in water, and distinguished by its affinity for the Vegetable fiber. In testimony whereof, we aifix our signatures.

LEOPOLD LASKA. OSKAR HALLER. 

